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WO1994000234A1 - Procede de delignification et de blanchiment d'une matiere lignocellulosique - Google Patents

Procede de delignification et de blanchiment d'une matiere lignocellulosique Download PDF

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Publication number
WO1994000234A1
WO1994000234A1 PCT/FR1993/000613 FR9300613W WO9400234A1 WO 1994000234 A1 WO1994000234 A1 WO 1994000234A1 FR 9300613 W FR9300613 W FR 9300613W WO 9400234 A1 WO9400234 A1 WO 9400234A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxidant
lignocellulosic material
iii
representing
catalyst
Prior art date
Application number
PCT/FR1993/000613
Other languages
English (en)
French (fr)
Inventor
Jean-François BOE
Jean-Jacques Girerd
Claude Guignard
Jean-Louis Seris
Jean-Baptiste Verlhac
Original Assignee
Elf Aquitaine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Aquitaine filed Critical Elf Aquitaine
Priority to US08/356,283 priority Critical patent/US5630906A/en
Priority to BR9306591A priority patent/BR9306591A/pt
Priority to AU43333/93A priority patent/AU671284B2/en
Priority to EP93913166A priority patent/EP0647158B1/fr
Priority to JP6502092A priority patent/JPH08500856A/ja
Priority to DE69313284T priority patent/DE69313284D1/de
Publication of WO1994000234A1 publication Critical patent/WO1994000234A1/fr
Priority to FI945990A priority patent/FI945990L/sv

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1078—Bleaching ; Apparatus therefor with Mn-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese

Definitions

  • the present invention relates to a process for the delignification and bleaching of a lignocellulosic material with an aqueous solution of an oxidant and of a redox catalyst.
  • the invention therefore relates to the technical field of wood and pulp and also to that of natural or synthetic redox catalysts. Many works relate to processes of degradation of lignin of wood or pulp.
  • Mn peroxidases oxidize Mn cations to Mn. Mn cations diffuse in wood structures and capture an electron to give Mn back
  • an oxidant chosen from hydrogen peroxide or tert-butyl hydroperoxide (HTB), in an aqueous medium.
  • the chosen Kraft pulp treated with a ferric hemine / HTB sees its Kappa number decrease from 36 to 2 with an elimination of 100% of lignin and only 10% of cellulose.
  • this porphyrin comprises 16 chlorine atoms substituting the phenyl and pyrrole nuclei and 4 sulfonato groups and that its synthesis is very expensive.
  • the replacement of iron by manganese in this porphyrinic structure does not change significantly the results.
  • veratrylic alcohol With veratrylic alcohol, if hydrogen peroxide is added to the preceding reaction medium, about 3 times less veratrylic aldehyde is obtained.
  • Hodgson et al, Inorganica Chemical Acta 141 (1988) 167-168 reviews synthetic manganese two-atom complexes and describes, in particular, some in which the metal is in high oxidation states.
  • TPA is a tetradentated ligand constituted by the tris (pyridinyl-2-methyl) amino.
  • the complex (I) is obtained by mixing TPA and Mn SO in water. H 2 0, then adding hydrogen peroxide. By adding sodium dithionate, the salt ((TPA) MnO]
  • ligands L, L, L_, L lead to complexes of Mn, of the type mentioned above and catalyze the epoxidation of cyclohexene in the presence of iodosobenzene acting as primary oxidant.
  • Patent application EP 0458398 (UNILEVER NV and PLC) reports a bleaching medium comprising a peroxy bleaching agent and a coordination complex of the manganese (or a precursor thereof) for use in the washing and bleaching of substrates, in particular textile laundering or dishwashing.
  • This last coordination complex has the general formula (A):
  • - Mn is manganese in the oxidation state IV
  • - n and m independently are whole numbers from 2 to 8
  • - X can represent a coordination or bridging group such as H, 0O ,, OOHH “ ,, 00 22 2 2 “ - ,, O0 2 2 " - ,, HHOO .--, SH-, S2 -, - SO -,
  • Y is a counter ion whose type depends on the charge z of the complex; if z is positive then Y represents an anion such as Cl ⁇ , Br-, I-, N0 3 -, Cl ⁇ -, NCS-, PF 6 -, RS ⁇ 3 -RS ⁇ 4 -, CF 3 S ⁇ 3 ⁇ 'BPh 4 - or OAc ⁇ ; if z is negative, when Y is a cation of an alkali or alkaline earth metal or a cation
  • L is ligand which is an organic molecule containing a number of hetero atoms (N, P, O and S) some of which coordinate the manganese atoms.
  • N, P, O and S hetero atoms
  • a preferred class of L ligands which correspond to formula (C) are tridentate ligands coordinating each manganese center (IV) with 3 nitrogen atoms N.
  • the peroxy bleaching agents used include hydrogen peroxide (H_0), compounds releasing or generating H O, in particular sodium perborate, peroxy acids and their salts.
  • Oxygen for example, is not very selective and also strongly degrades cellulose in NaOH medium and, to a lesser degree, in the presence of magnesium salts.
  • Chlorine is a relatively selective delignification agent. Under the acid conditions used, it causes oxidation but also electrophilic substitution of the aromatic nuclei of lignin, producing dicarboxylic acids and chlorinated fragments of lignin. These represent a potential danger to the environment.
  • Hydrogen peroxide is mainly used in basic medium.
  • This basic medium causes a certain depolymerization of the cellulose.
  • the aim of the present invention is to develop a new means for delignification and bleaching of lignocellulosic materials suspended in a medium. aqueous.
  • Another more specific aim is to avoid the nucleophilicity of chlorine in the bleaching of paper pulp in order to eliminate the potential environmental problems linked to TOX ("total organically bound halogens").
  • a third aim is to use oxygenated oxidants such as ozone, hydrogen peroxide or their mixtures, in delignification and bleaching in an acidic or neutral aqueous medium by adjusting the oxidation potential of this medium to a chosen value.
  • the present invention is a process for the delignification and bleaching of a lignocellulosic material in suspension in an aqueous medium comprising an oxidizing agent and an oxidoreduction catalyst chosen from a family of liganded manganese complexes, some of which have already been described, in particular by DJHodgson. et al.
  • the present invention is a process for the delignification and bleaching of a lignocellulosic material in which an aqueous solution of a redox catalyst and an oxidant is reacted on said material, characterized in that said catalyst comprises a cation organometallic of general formula (VII):
  • Mn manganese in an oxidation state III or IV, the two Mn of this cation being able to form a pair of oxidation state III-III or III-IV or IV-IV, n is 2.3 or, O representing oxygen, L represents a ligand of general formula (VIII): in which: let R ⁇ represent the radical:
  • R 2 then representing the radical:
  • R3 R'3 and R 1 1] each representing, independently of each other, a group selected from hydrogen, lower C] _ to C4 alkyl, lower alkoxy, C ⁇ to C4 alkyl, halogen, or R] ⁇ represents The radical:
  • R 2 and R ' 2 then being identical and representing a group chosen from hydrogen, lower alkyl in C ⁇ to C4, R3 representing a group chosen from hydrogen, lower alkyl in C j _ to C4, lower alkoxy in C j _ to C4 , halogen.
  • This process has the advantage that the organometallic cation (VII) is very stable with respect to the oxidizing power of the medium and that the solution containing it after reaction can be recovered and reacted with a new batch of lignocellulosic material to which has been added with oxidant.
  • the pH of the aqueous solution is less than 7 and preferably between 2 and 5.
  • the latter in order to remove by extraction the oxidation products of the lignocellulosic material, the latter, after the oxidation reaction ((VII) + oxidant), is treated with a basic aqueous solution.
  • the oxidant is chosen from ozone, hydrogen peroxide, an alkyl hydroperoxide, hypochlorous acid, chlorine, chlorine dioxide or mixtures thereof.
  • the selection criterion for these oxidants consists in determining their ability to give the cation of general formula (VII) in which the two manganese atoms are in the oxidation states III-III or III-IV or IV-IV.
  • State III-III is not always isolated for all complexes.
  • L is TPA
  • the oxidation state obtained in the synthesis of this complex where the hydrogen peroxide intervenes is III-IV
  • L is the ((6-methyl-2- pyridyl) methyl)) (2- (2- pyridyl) ethyl) (2-pyridylmethyl) amine (L3)
  • the cation (VII) obtained by the action of hydrogen peroxide is III-IV.
  • the chemical oxidation of this complex by NaOCl placed in an acid medium gives the state of IV-IV oxidation.
  • the preferred combinations of the redox cations of general formula (VII) with the oxidants are those which lead to an oxidation state III-IV and / or IV / IV.
  • the oxidant is added little by little to the solution of the redox catalyst (VII) in the presence of the paste, so that there is no excess of oxidant which can react directly with the lignocellulosic material.
  • VI redox catalyst
  • the oxidation potential is then somehow buffered to that of the redox catalyst (VII) in its state III-IV or, as the case may be, IV-IV, knowing that the oxidation potential of the oxidant is in principle always greater than that of the redox catalyst.
  • the lignocellulosic material reacted is advantageously fragmented wood or pulp containing lignin.
  • each group R 3 , R ⁇ , ⁇ '' 3 is in the para position relative to the doublet of pyridine nitrogen.
  • each group R 3 , * 3 # R '' 3 and chosen from lower alkyl and lower alkoxy.
  • the weight ratio of the redox catalyst to the lignocellulosic material is between 0.1 and 10%.
  • the temperature of said aqueous oxidant and catalyst solution is between 80 and 100 ° C.
  • the molar ratio of oxidizing catalyst is between 0.1 and 4 %.
  • the weight ratio of the lignocellulosic material to the oxidant is between 2 and 100.
  • R represents a group chosen from H, lower alkyl, lower alkoxy, halogen, R is in position 3,4,5 or 6, on the pyridine ring, and preferably in position 4.
  • the different groups X above can be obtained by known reactions, one from the other, by functionalization, reduction or oxidation.
  • the catalysts (VII) in which n is 2 or 3 are obtained by mixing in 1 * water a salt comprising the cation Mn 2+ in particular provided by MnSO or MnCl with a ligand L (VIII) in the presence of hydrogen peroxide, according to the procedures described by DJ Hodgson (see above).
  • the complexes (VII) in which n is 4 are obtained by oxidizing the corresponding complexes in which n is 2 or 3 by oxidants more powerful than hydrogen peroxide, for example, hypochlorous acid
  • HC10 chlorine dioxide
  • C10_ chlorine dioxide
  • K Kappa index
  • DP degree of polymerization of the cellulose
  • the determination of the Kappa index an objective measurement of the lignin contained in the pulp, is carried out as follows: the lignin is oxidized with KMnO. in a weakly acid medium.
  • the kappa index is defined [according to the standard NF / 150-302] as the number of milliliters of a 0.02 M solution of KMnO necessary for the complete oxidation of one gram (dry weight) of paper pulp.
  • a Kappa point therefore represents: 10 ⁇ 3 x (0.02 x 5) xe or O, 1 m electronic equivalent / g of dough.
  • the method for measuring the degree of polymerization consists in measuring the specific viscosity of a paste solution in cupri-ethylene diamine and in deducing therefrom the average degree of polymerization (DP), according to French standard NF T 12 005 (March 1953 ).
  • the pasta is washed beforehand with water (90 ° C, 20 min) dried in an oven (50 ° C, under vacuum), then is the subject of a first determination of the Kappa index and the DP.
  • the two pastes used then have the following characteristics collated in Table 3.
  • N, N'-Dimethylethylenediamine is commercial, the other diamines are obtained according to the publication "Helvetica Chim. Acta, 51_, 1974, p.1036.
  • the substituted chloromethyl-pyridines are prepared from the corresponding N-oxide compounds according to the references following:
  • Diamines can be transformed into their hydrochlorides by bubbling HCl gas into their ethereal solution.
  • the tests are carried out at different temperatures (60 ° C, 80 ° C, 90 ° C, 98 ° C, for a fixed period.
  • the dough is placed for 1 hour in a 0.25 M sodium hydroxide solution at 60 ° C.
  • the purpose of this operation is to extract from the pulp the fragmented compounds, phenols and carboxylates, soluble in the hot alkaline solution.
  • the dough thus treated is washed thoroughly with water in order to remove all basic traces, wrung and dried in an oven (50 ° C) under vacuum.
  • a new determination is then made of the Kappa index and possibly also of the DP.
  • Table 4 collates the H 0 contents and the Kappa indices obtained with or without manganese, at a temperature of 90 ° C., for an oxidation time of 3 hours and at a pH of 3.5.
  • step 1 The effects of the temperature of the reaction medium of the delignification and bleaching step (step 1), similar to that of Example 1, were studied, the pH being 3.5, the initial content of H_0 being 1.85 mmol / g of dough A for an oxidation time of 5 h.
  • step 1) The effects of the duration of step 1) were studied, the conditions being for the other parameters identical to those of Example 3, the temperature being 90 ° C. The results appear in Table 7:
  • reaction medium is separated from the paper pulp by filtration.
  • the kappa index is determined on the treated dough, the reaction medium is brought into contact with a new batch of dough. A new solution of hydrogen peroxide is introduced continuously. It is estimated that 40 to 50% of the catalyst is recovered after each cycle.
  • stage 1 The influence of the experimental conditions of the oxidation stage (stage 1) was studied on the dough A and results from the results appearing in table 12 below: TABLE 12
  • An unbleached hardwood pulp having a Kappa index equal to 13 is subjected to the same steps as in Example 1, but with ligands of the Bispicen type.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Catalysts (AREA)
PCT/FR1993/000613 1992-06-22 1993-06-21 Procede de delignification et de blanchiment d'une matiere lignocellulosique WO1994000234A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US08/356,283 US5630906A (en) 1992-06-22 1993-06-21 Process for the delignifcation and bleaching of a lignocellulose material
BR9306591A BR9306591A (pt) 1992-06-22 1993-06-21 Processo de deslignificação e de branqueamento de uma matéria lignocelulósica
AU43333/93A AU671284B2 (en) 1992-06-22 1993-06-21 Method for delignifying and bleaching a lignocellulose material
EP93913166A EP0647158B1 (fr) 1992-06-22 1993-06-21 Procede de delignification et de blanchiment d'une matiere lignocellulosique
JP6502092A JPH08500856A (ja) 1992-06-22 1993-06-21 リグノセルロース材料の脱リグニン及び漂白方法
DE69313284T DE69313284D1 (de) 1992-06-22 1993-06-21 Verfahren zur deliquifizierung und zum bleichen von einem ligenocellulosischen material
FI945990A FI945990L (sv) 1992-06-22 1994-12-21 Förfarande för delignifiering och blekning av ett lignocellulosamaterial

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR92/07577 1992-06-22
FR9207577A FR2692499B1 (fr) 1992-06-22 1992-06-22 Procédé de délignification et de blanchiment d'une matière lignocellulosique.

Publications (1)

Publication Number Publication Date
WO1994000234A1 true WO1994000234A1 (fr) 1994-01-06

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US (1) US5630906A (sv)
EP (1) EP0647158B1 (sv)
JP (1) JPH08500856A (sv)
AT (1) ATE157024T1 (sv)
AU (1) AU671284B2 (sv)
BR (1) BR9306591A (sv)
CA (1) CA2138797A1 (sv)
DE (1) DE69313284D1 (sv)
FI (1) FI945990L (sv)
FR (1) FR2692499B1 (sv)
NZ (1) NZ253184A (sv)
WO (1) WO1994000234A1 (sv)

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WO1997044520A1 (en) * 1996-05-20 1997-11-27 Rudolf Patt A method for the delignification of fibrous material and use of a catalyst
FR2813896A1 (fr) * 2000-09-14 2002-03-15 Atofina Procede de delignification et blanchiment par un oxydant et un catalyseur d'oxydoreduction
EP2726670A1 (en) * 2011-06-30 2014-05-07 Nano-Green Biorefineries Inc. Catalytic biomass conversion
US11168151B2 (en) 2016-01-28 2021-11-09 Nano-Green Biorefineries Inc. Production of crystalline cellulose

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FR2741340B1 (fr) * 1995-11-16 1997-12-26 Elf Aquitaine Procede d'oxydation de substrats organiques en presence de complexes metalliques de ligands tetra-, penta- et hexacoordinants et catalyseurs d'oxydation les contenant
DE19614587A1 (de) * 1996-04-13 1997-10-16 Jaschinski Thomas Dipl Holzw Verfahren und Bleichlösung zum Bleichen von cellulosischen Faserstoffen
BR9709798A (pt) * 1996-06-19 1999-08-10 Unilever Nv Catalisador de alvejamento e oxidacão sistema de oxidacão catalítica e composicão de alvejamento
CA2248476A1 (en) * 1997-10-01 1999-04-01 Unilever Plc Bleach activation
EP1008645B1 (en) * 1998-11-10 2004-07-21 Unilever Plc Detergent bleaching compositions
DE69817832T2 (de) * 1998-11-10 2004-10-07 Unilever Nv Bleich- und Oxidationskatalysator
KR100555040B1 (ko) * 1998-12-29 2006-05-16 주식회사 엘지생활건강 트리스(2-피리딜메틸)아민 망간 착화합물과 이를 함유한 표백제및 표백세제 조성물
CA2326311A1 (en) * 1999-11-19 2001-05-19 Praxair Technology, Inc. Method for applying activated ozone in pulp bleaching
US8216809B2 (en) * 2008-12-19 2012-07-10 E I Du Pont De Nemours And Company Organic solvent pretreatment of biomass to enhance enzymatic saccharification
US20100159522A1 (en) * 2008-12-19 2010-06-24 E.I. De Pont De Nemours And Company Organosolv and ozone treatment of biomass to enhance enzymatic saccharification
US20100159515A1 (en) 2008-12-19 2010-06-24 E.I. Du Pont De Nemours And Company Oxidative pretreatment of biomass to enhance enzymatic saccharification
WO2010080489A1 (en) * 2008-12-19 2010-07-15 E. I. Du Pont De Nemours And Company Ozone treatment of biomass to enhance enzymatic saccharification
MX2011012494A (es) 2009-05-28 2012-02-21 Gp Cellulose Gmbh Celulosa modificada a partir de fibra kraft quimica y metodos para elaborarla y su uso.
US9512237B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Method for inhibiting the growth of microbes with a modified cellulose fiber
US9511167B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Modified cellulose from chemical kraft fiber and methods of making and using the same
US9512563B2 (en) 2009-05-28 2016-12-06 Gp Cellulose Gmbh Surface treated modified cellulose from chemical kraft fiber and methods of making and using same
WO2012091965A1 (en) 2010-12-17 2012-07-05 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
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US20140275420A1 (en) 2011-08-22 2014-09-18 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
ES2844150T3 (es) 2012-01-12 2021-07-21 Gp Cellulose Gmbh Una fibra al sulfato de baja viscosidad que tiene propiedades de amarilleamiento reducidas y métodos para elaborar y usar la misma
WO2013123513A1 (en) * 2012-02-17 2013-08-22 PHARMA, Thinq Use of metalloporphyrins and salen complexes for the catalytic oxidation of organic compounds
WO2013126745A2 (en) * 2012-02-23 2013-08-29 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US8871051B2 (en) * 2012-03-21 2014-10-28 Los Alamos National Security, Llc Process for decomposing lignin in biomass
CN106968127B (zh) 2012-04-18 2019-03-01 Gp纤维素股份有限公司 用于粘胶溶液的针叶木牛皮纸浆
AU2014213691B2 (en) 2013-02-08 2017-03-16 Gp Cellulose Gmbh Softwood kraft fiber having an improved a-cellulose content and its use in the production of chemical cellulose products
BR112015019882A2 (pt) 2013-03-14 2017-07-18 Gp Cellulose Gmbh fibra kraft clareada oxidada e métodos para fazer polpa kraft e fibra kraft de madeira macia e para clarear polpa kraft de celulose em sequência de branqueamento de multi-estágios
MX372579B (es) 2013-03-15 2025-03-04 Gp Cellulose Gmbh Una fibra kraft de baja viscosidad que tiene un contenido de carboxilo mejorado, y metodos para fabricar y usar la misma
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
AR104939A1 (es) * 2015-06-10 2017-08-23 Chemsenti Ltd Método oxidativo para generar dióxido de cloro
AR104940A1 (es) * 2015-06-10 2017-08-23 Chemsenti Ltd Método para generar dióxido de cloro
CA3040734A1 (en) 2016-11-16 2018-05-24 Gp Cellulose Gmbh Modified cellulose from chemical fiber and methods of making and using the same
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes

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EP0350395A1 (fr) * 1988-07-06 1990-01-10 Societe Nationale Elf Aquitaine Procédé d'oxydation par catalyse biomimétique d'alcools benzyliques et de composés apparentés
US5153161A (en) * 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
EP0458397B1 (en) * 1990-05-21 1997-03-26 Unilever N.V. Bleach activation

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SE466061B (sv) * 1990-04-23 1991-12-09 Eka Nobel Ab Blekning av kemisk massa genom behandling med foerst ett komplexbildande aemne och sedan ett peroxidinnehaallande aemne

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0350395A1 (fr) * 1988-07-06 1990-01-10 Societe Nationale Elf Aquitaine Procédé d'oxydation par catalyse biomimétique d'alcools benzyliques et de composés apparentés
EP0458397B1 (en) * 1990-05-21 1997-03-26 Unilever N.V. Bleach activation
US5153161A (en) * 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997044520A1 (en) * 1996-05-20 1997-11-27 Rudolf Patt A method for the delignification of fibrous material and use of a catalyst
FR2813896A1 (fr) * 2000-09-14 2002-03-15 Atofina Procede de delignification et blanchiment par un oxydant et un catalyseur d'oxydoreduction
WO2002022944A1 (fr) * 2000-09-14 2002-03-21 Atofina Procede de delignification et blanchiment par un oxydant et un catalyseur d'oxydoreduction
EP2726670A1 (en) * 2011-06-30 2014-05-07 Nano-Green Biorefineries Inc. Catalytic biomass conversion
EP2726670A4 (en) * 2011-06-30 2015-03-25 Nano Green Biorefineries Inc CATALYTIC CONVERSION OF BIOMASS
US9388251B2 (en) 2011-06-30 2016-07-12 Nano-Green Biorefineries Inc. Catalytic biomass conversion
US11168151B2 (en) 2016-01-28 2021-11-09 Nano-Green Biorefineries Inc. Production of crystalline cellulose

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Publication number Publication date
EP0647158B1 (fr) 1997-08-20
NZ253184A (en) 1995-09-26
FR2692499A1 (fr) 1993-12-24
EP0647158A1 (fr) 1995-04-12
FI945990L (sv) 1995-02-21
ATE157024T1 (de) 1997-09-15
FI945990A0 (sv) 1994-12-21
CA2138797A1 (fr) 1994-01-06
FR2692499B1 (fr) 1994-08-26
BR9306591A (pt) 1998-12-08
US5630906A (en) 1997-05-20
JPH08500856A (ja) 1996-01-30
AU4333393A (en) 1994-01-24
DE69313284D1 (de) 1997-09-25
AU671284B2 (en) 1996-08-22

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